WO2022063993A1 - Procédé de conversion alternatif du méthanol en oléfines (mto) - Google Patents

Procédé de conversion alternatif du méthanol en oléfines (mto) Download PDF

Info

Publication number
WO2022063993A1
WO2022063993A1 PCT/EP2021/076372 EP2021076372W WO2022063993A1 WO 2022063993 A1 WO2022063993 A1 WO 2022063993A1 EP 2021076372 W EP2021076372 W EP 2021076372W WO 2022063993 A1 WO2022063993 A1 WO 2022063993A1
Authority
WO
WIPO (PCT)
Prior art keywords
stream
olefins
oxygenates
olefin stream
olefin
Prior art date
Application number
PCT/EP2021/076372
Other languages
English (en)
Inventor
Pablo Beato
Original Assignee
Haldor Topsøe A/S
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Haldor Topsøe A/S filed Critical Haldor Topsøe A/S
Priority to EP21782977.9A priority Critical patent/EP4217446A1/fr
Priority to US18/245,828 priority patent/US20240026236A1/en
Priority to CN202180064887.9A priority patent/CN116194557A/zh
Publication of WO2022063993A1 publication Critical patent/WO2022063993A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step
    • C10G69/126—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step polymerisation, e.g. oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/08—Jet fuel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/22—Higher olefins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Definitions

  • SAF sustainable aviation fuel
  • Potential feedstocks for producing SAFs are generally classified as (a) oil-based feedstocks, such as vegetable oils, waste oils, algal oils, and pyrolysis oils; (b) solid-based feedstocks, such as lignocellulosic biomass (including wood products, forestry waste, and agricultural residue) and municipal waste (the organic portion); or (c) gas-based feedstocks, such as biogas and synthesis gas (syngas). Syngas, alcohols, sugars, and bio-oils can be further upgraded to jet fuel via a variety of synthesis, either fermentative or catalytic processes.
  • oil-based feedstocks such as vegetable oils, waste oils, algal oils, and pyrolysis oils
  • solid-based feedstocks such as lignocellulosic biomass (including wood products, forestry waste, and agricultural residue) and municipal waste (the organic portion)
  • gas-based feedstocks such as biogas and synthesis gas (syngas). Syngas, alcohols, sugars, and bio-oils can be further upgraded to
  • US 4,021,502, US 4,211,640, US 4,22,7992, US 4,433,185, US 4,456,779 disclose process layouts based on classical MTO process conditions, i.e. high temperatures e.g. about 500°C and moderate pressures e.g. about 1-3 bar, in order to obtain efficient conversion of methanol to olefins.
  • high temperatures e.g. about 500°C
  • moderate pressures e.g. about 1-3 bar
  • aromatic hydrocarbons aromatic hydrocarbons
  • MOGD Mobil-Olefin-to-Gasoline-Distillates
  • US 9,957,449 discloses a process for the producing hydrocarbons in the jet fuel range by oligomerization of renewable olefins having three to eight carbons.
  • US 8,524,970 discloses a process for producing diesel of better quality, i.e. diesel with a higher cetane number comprising conversion of oxygenates to olefins, oligomerization of olefins and subsequent hydrogenation.
  • US 20190176136 discloses the use of a ZSM-23 zeolite as catalyst for methanol to olefin conversion in a process step which is conducted at atmospheric pressure (about 1 bar) and 400°C, thereby producing a hydrocarbon stream with less than 5wt% aromatics.
  • US 7,482,300 discloses a composition comprising ZSM-48 crystals having a silica:alu- mina molar ratio of 110 or less, or at least 70, which is free of non-ZSM-48 seed crystals and free of ZSM-50.
  • the composition is used for catalytic dewaxing.
  • US 2017/0121237 A1 discloses a process for converting oxygenate containing feedstocks to gasoline and distillates, in which methanol conversion catalysts is selected from a wide range of zeolites, including ZSM-48 and at the conditions of pressure being between 15 and 90 psig and the temperature being above 450°C.
  • US 4,476,338 discloses a process for converting methanol and/or dimethyl ether to olefins comprising a major fraction of light olefins, at moderate temperature and atmospheric pressure comprising contacting the feed with an alumina crystalline zeolite catalyst designated as ZSM-48.
  • ZSM-48 alumina crystalline zeolite catalyst designated as ZSM-48.
  • This citation teaches (Ex. 1-2, Table 2) the use of ZSM-48 with a silica-to-alumina ratio (SAR) higher than 110, more specifically 113 or 180, and where methanol is converted over the zeolite catalyst at atmospheric pressure and a moderate temperature of 370°C.
  • SAR silica-to-alumina ratio
  • WO 2018/071905 A1 discloses the conversion of C2-C8 olefins to jet fuel and/or diesel fuel in high-yield from bio-based alcohols.
  • US 4613719 A discloses oligomerization of olefins in a process for converting lower olefins to higher hydrocarbons used as liquid fuels.
  • MTO methanol to olefins
  • oxygenate such as methanol to olefins
  • OU means oligomerization
  • Hydro means hydrogenation
  • Hydro/OLI means a single combined step comprising hydrogenation and oligomerization.
  • MTO overall process
  • OLI overall process and plant
  • jet fuel and “hydrocarbons boiling in the jet fuel range” are used interchangeably and have the meaning of a mixture of C8-C16 hydrocarbons boiling in the range of about 130-300° at atmospheric pressure.
  • SAF sustainable aviation fuel or aviation turbine fuel, in compliance with ASTM D7566 and ASTM D4054.
  • olefin stream means a hydrocarbon stream rich in olefins comprising higher and lower olefins, and optionally also aromatics, paraffins, iso-paraffins and naphthenes, and in which the combined content of higher and lower olefins is at least 25 wt%, such as 30 wt% or 50 wt%.
  • the term “high content of higher olefins” means that the weight ratio in the olefin stream of higher olefins to lower olefins is above 1, suitably above 10, for instance 20-90 such as 70-80.
  • the term “low content of higher olefins” means that the weight ratio in the olefin stream of higher olefins to lower olefins is 10 or below, such as 1 or below.
  • the term “selectivity to higher olefins” means the weight ratio of higher to lower olefins. “High selectivity to higher olefins” or “higher selectivity to higher olefins” means a weight ratio of higher to lower olefins of above 1 , suitably above 10.
  • the term is also used interchangeably with the term “light paraffins”.
  • the term “essentially free or ethylene” or “free of ethylene” means 1 wt% or lower.
  • the term “essentially free of aromatics”, “substantially free of aromatics”, “aromatic-free” or “low aromatics” means less than 5 wt%, e.g. 1 wt% or even less than 1 wt%.
  • Aromatics include benzene (B), toluene (T), xylene (X) and ethylbenzene.
  • partial conversion of the oxygenates or “partly converting the oxygenates” means a conversion of the oxygenates of 20-80%, for instance 40-80%, or 50-70%.
  • the term “full conversion of the oxygenates” or “fully converting the oxygenates” means above 80% conversion of the oxygenates, for instance 90% or 100%.
  • the term “substantial methanol conversion” is used interchangeably with the term “full conversion of the oxygenates”, where the oxygenate is methanol.
  • catalyst comprising a zeolite and “zeolite catalyst” are used interchangeably.
  • sica to alumina ratio means the mole ratio of SiC>2 to AI2O3.
  • the term “significant amount of paraffins” means 5-20 wt%, such as IQ- 15 wt% in the olefin stream.
  • MTO methanol to olefins
  • the invention is a process for producing an olefin stream comprising passing a feedstock stream comprising oxygenates over a catalyst active in the conversion of oxygenates, thereby forming an olefin stream, said process comprising the steps of: passing the feedstock stream comprising oxygenates through a first reactor set including a single reactor or several reactors for the partial or full conversion of the oxygenates, and through a second reactor set including a single reactor or several reactors for the further conversion of the oxygenates and a phase separation stage in between the first reactor set and the second reactor set, for thereby forming the olefin stream.
  • the first reactor set is used for the passing therethrough of the feedstock comprising oxygenates thereby providing partial or full conversion of the oxygenates
  • the second reactor set is used for the passing therethrough of the feedstock or a portion thereof after the partial or full conversion of the oxygenates and passage through the separation stage.
  • the several reactors in the first reactor set are mutually arranged in parallel.
  • the entire feedstock stream passes through the first reactor set, i.e. there is no substantial splitting of the feedstock stream.
  • the term “entire feedstock” means at least 90 wt% of the feedstock.
  • the process further comprises:
  • the feedstock stream comprising oxygenates through the first reactor set under conditions for partly converting, e.g. 40-80% such as 60-70% conversion, the oxygenates, thereby forming a raw olefin stream comprising unconverted oxygenates and C2-C8 olefins particularly C3-C8 olefins, e.g. the raw olefin stream may comprise water, methanol and C2-C8 olefins, particularly C3-C8 olefins;
  • a first olefin stream which is rich in lower olefins
  • a separated oxygenate stream comprising the unconverted oxygenates, e.g. the separated oxygenate stream may comprise water and methanol
  • a second olefin stream which is rich in higher olefins
  • the olefin stream i.e. olefin product stream
  • the olefin stream is suitably also free of ethylene e.g. less than 1 wt%, while having a significant content of isoparaffins e.g. 10-15 wt%.
  • the process enables increased flexibility in the handling of a variety of feedstocks comprising oxygenates, including fatty acids in renewable feeds, or oxygenates originating from one or more of a biological source, as well as the handling of, optionally, different types in catalysts in the two different sets of reactors.
  • the process further comprises adding an olefin stream comprising lower olefins, preferably being an olefin stream comprising C2-C3 olefins, more preferably a C3-olefin stream as co-feed to the first and/or second reactor set.
  • the process comprises recycling to the first and/or second reactor set a portion of the olefin stream, said portion of the olefin stream preferably being an olefin stream comprising C2-C3 olefins, more preferably a C3-olefin stream, which is withdrawn from said olefin stream, i.e. the olefin product stream from the second reactor set.
  • the portion of the olefin stream is for instance recycled to said combined stream comprising lower olefins and the unconverted oxygenates and which is fed to the second reactor set.
  • the portion of the olefin stream is for instance recycled to the feedstock stream comprising oxygenates which is fed to the first reactor set.
  • the process further comprises recycling a portion of the olefin stream to the feedstock stream and using it as additional feed stream, i.e. as a co-feed, and which may include recycling light paraffins, including methane, acting as a diluent, and reducing the adiabatic temperature increase, e.g. by combining with the feedstock stream comprising oxygenates.
  • additional feed stream i.e. as a co-feed
  • additional feed stream i.e. as a co-feed
  • the concentration of higher olefins in the olefin stream is further increased while also having full utilization of the less desired lower olefins for conversion into higher olefins.
  • Any undesired cracking of higher olefins in the process is contained by recycling products of such cracking, namely C2-C3 olefins, back to the feed.
  • this recycle suitably also containing light paraffins and optionally also isoparaffins, further provides a dilution effect on the feedstock stream, thereby enabling better control of the exothermicity during the conversion to olefins.
  • the co-feed stream i.e. the recycle stream
  • the co-feed stream is between 1 to 20 times, such as 2 to 10 times, the volumetric amount of the feedstock stream e.g. methanol feed stream to the first reactor set.
  • the recycle stream contains is 0.5-10% or 1-10% mol propylene and the concentration of methanol in the feed is 10 vol.%.
  • catalyst longevity or “catalyst lifetime” comprises not only overall lifetime of the catalyst (number of cycles), but also the lifetime during each cycle, i.e. cycle time.
  • cycle time also known as “cycle length” is the length of the period where the catalyst exhibits proper catalytic activity, and which is typically measured as hours-on-stream (HOS). From a process point of view this is highly beneficial, since the recycle stream of C2-C3 olefins will also enable easier control of the exothermicity of the MTO.
  • the feed to the second reactor set is a combined stream comprising lower olefins, e.g. C2-C3 olefins and the unconverted oxygenates.
  • the invention provides an inherent addition of such co-feed (stream comprising C2-C3 olefins) to the second reactor set, where full conversion is desired.
  • the benefits associated with co-feeding a stream comprising C2-C3 olefins, suitably a C3-olefin stream (propylene) in the MTO e.g. the first reactor set, are therefore already inherent in the process of the invention in connection with the feed to the second reactor set. Additional C2-C3 olefins may still be provided, e.g. by providing said recycle of a portion of the olefin stream.
  • the first reactor set consists of 2-4 reactors, such as 3 reactors, and the second reactor set consists of 1-3 reactors, such as 2 reactors.
  • the reactors are preferably mutually arranged in parallel.
  • many reactors are run in parallel, e.g. five (5) reactors.
  • the present invention it is possible to replace the 5 reactors in parallel by for instance the first reactor set consisting of three reactors, and the second reactor set consisting of two reactors.
  • the first three reactors at e.g. only 70% conversion, and then further convert the unconverted oxygenates, e.g. methanol, together the C2- C3 olefins, to 100% in two reactors arranged in series to the first three.
  • the temperature in all five reactors is lowered, yet full conversion is achieved. Flexibility is also improved, by enabling that one reactor may be taken out of service for regeneration.
  • first reactor set and second reactor set are arranged in series.
  • the olefin stream resulting from the process may contain higher olefins and/or lower olefins, as well as high and/or low content of aromatics.
  • the process conditions such as pressure and temperature are adapted for obtaining an olefin stream which for instance is substantially free in aromatics and has a low content of higher olefins, or an olefin stream which is substantially free in aromatics and has a high content of higher olefins, suitably also free of ethylene and optionally having a significant amount of isoparaffins.
  • the matrix table below shows the range of possibilities:
  • the olefin stream may comprise low aromatics as well as lower and higher olefins.
  • the olefin stream may also comprise high aromatics as well as lower and higher olefins.
  • An olefin stream containing e.g. a high content of aromatics, for instance more than IQ- 20 wt% aromatics, is still a suitable oligomerization feed, since the final blend in the jet fuel may contain aromatics and/or these aromatics may also be converted to jet fuel in the subsequent oligomerization and hydrogenation steps.
  • the catalyst comprises a zeolite having a structure selected from MFI, MEL, SZR, SVR, ITH, IMF, TUN, FER, EUO, MSE, *MRE, MWW, TON, MTT, AFO, AEL, and combinations thereof, preferably a zeolite with a framework having a 10-ring pore structure i.e. pore circumference defined by 10 oxygens, such as zeolites having a structure selected from TON, MTT, MFI, *MRE, MEL, AFO, AEL, EUO, FER, and combinations thereof.
  • temperature means the MTO reaction temperature in an isothermal process, or the inlet temperature to the MTO in an adiabatic process.
  • the catalyst may be formed by combining the zeolite with a binder, and then forming the catalyst into pellets.
  • the pellets may optionally be treated with a phosphoric reagent to create a zeolite having a phosphorous component between 0.5 and 15 wt % of the treated catalyst.
  • the binder is used to confer hardness and strength on the catalyst. Binders include alumina, aluminum phosphate, silica, silica-alumina, zirconia, titania and combinations of these metal oxides, and other refractory oxides, and clays such as montmorillonite, kaolin, palygorskite, smectite and attapulgite.
  • a preferred binder is an aluminum-based binder, such as alumina, aluminum phosphate, silica-alumina and clays.
  • the process is conducted at a pressure of 1-60 bar and a temperature of 125-700°C.
  • These conditions further specify the process requirements for achieving the above range of possibilities regarding content of aromatics and olefins.
  • higher temperatures result in higher content of lower olefins.
  • the process is conducted over a catalyst comprising a zeolite with a framework having a 10-ring pore structure, in which said 10-ring pore structure comprises (a) a unidimensional (1-D) pore structure, such as *MRE, for instance Ell-2, and/or (b) a three-dimensional (3-D) pore structure, such as MFI, for instance MFI modified with an alkaline earth metal, e.g. a Ca/Mg-modified ZSM-5, in particular a Ca- modified ZSM-5; and at a pressure of 1-50 bar and temperature of 150-600°C.
  • a 1-D pore structure means zeolites containing non-intersecting pores that are substantially parallel to one of the axes of the crystal. The pores preferably extend through the zeolite crystal.
  • a 3-D pore structure means zeolites containing intersecting pores that are substantially parallel to all three axes of the crystal. The pores preferably extend through the zeolite crystal.
  • Ca/Mg-modified ZSM-5 means a ZSM-5 modified with Ca and/or Mg.
  • the zeolite catalysts may be prepared by standard methods in the art. For instance, Ca and/or Mg are loaded in a commercially available ZSM-5 zeolite at concentrations of 1- 10 wt.%, such as 2, 4 or 6 wt.%, by ion-exchange e.g. solid-state ion-exchange; or wet impregnation e.g. incipient wetness impregnation or any other suitable impregnation.
  • ion-exchange e.g. solid-state ion-exchange
  • wet impregnation e.g. incipient wetness impregnation or any other suitable impregnation.
  • impregnation of the final catalyst with binder/matrix such as in a catalyst that contains up to 30-90 wt% zeolite, such as 50-80 wt% zeolite in a matrix/binder comprising an alumina component such as a silica-alumina matrix binder.
  • binder is also referred to as “matrix binder” or “matrix/binder” or “binder/matrix”.
  • the catalyst comprises a zeolite having a (a) 1-D pore structure and/or (b) 3-D pore structure, the pressure is 1-50 bar such as 2-20 bar and the temperature is 500-550°C. This results in low aromatics and low content of higher olefins:
  • the catalyst comprises a zeolite having a (a) 1-D pore structure and/or (b) 3-D pore structure, the pressure is 1-50 bar, such as 2-20 bar or 5-10 bar, and the temperature is 150-480°C, such as 150-350°C, 200-300°C, or 250-350°C. In another embodiment, the pressure is 2-30 bar, for instance 2-20 bar or 5-10 bar, and the temperature is 340-400°C, for instance 340-385°C or 360-380°C. This results in low aromatics and high content of higher olefins:
  • the catalysts are active in not only suppressing the formation of aromatics, but also in providing a high selectivity for higher olefins as well as full conversion of the oxygenate feed.
  • the catalyst comprises a zeolite with a framework having a 10-ring pore structure, in which said 10-ring pore structure comprises a three-dimensional (3-D) pore structure, such as MFI, e.g. a Ca/Mg-modified ZSM-5, in particular a Ca-modified ZSM-5, and the temperature is in the range 340-400°C, a significant increase in higher olefins is observed as well as a sharp decrease in aromatics content, while still fully converting the oxygenates, e.g. methanol.
  • MFI three-dimensional
  • a Ca/Mg-modified ZSM-5 e.g. a Ca/Mg-modified ZSM-5
  • Ca-modified ZSM-5 e.g. a Ca-modified ZSM-5
  • the temperature is in the range 340-400°C
  • a suitable oligomerization feed may have some aromatics, for instance 10-20 wt% aromatics, as well as higher and lower olefins
  • the ideal oligomerization feed is namely substantially free of aromatics and composed of higher olefins, and preferably as little as possible C2-light fraction.
  • the olefin stream may e.g. comprise at least 20 wt% C4-C8 olefins, such as above 30 wt% C4-C8 olefins or above 40 wt% C4-C8 olefins and less than 10 wt% aromatics e.g. less than 5 wt% aromatics.
  • the oligomerization feed complies with the above ASTM requirements stipulating the 50% SAF blending part to be almost aromatic-free, more specifically that the content of aromatics be limited to below 0.5 wt%.
  • the olefin stream can be converted into such jet fuel via oligomerization and hydrogenation in a more efficient overall process due to i.a. less recycling and higher oligomerization yields.
  • the higher olefins and low selectivity to aromatics simplifies separation steps and increase overall yields of the jet fuel.
  • the low acid strength means that relatively high temperatures are necessary for achieving reasonable methanol conversions and such temperature increase would result in also increasing the rate of olefin cracking as mentioned above, thereby countering the effect of the increased pressure.
  • the pressure may be increased, and the temperature lowered, resulting in that it is still possible to maintain substantial methanol conversion, whilst at the same time achieving an olefin stream substantially free of aromatics and having a high content of higher olefins.
  • a reactor in the first reactor set and/or second reactor set operates at 2-30 bar, such as 5-15 bar, and at 150-480°C such as 150-350°C or 200- 300°C.
  • the zeolite has a 1-D pore structure and is any of *MRE (ZSM-48), MTT (ZSM-23), TON (ZSM-22), or combinations thereof; and optionally having a silica- to-alumina ratio (SAR) of up to 110, such as ZSM-48 having SAR up to 110; and the process is conducted at a pressure of 1-25 bar such as 1-15 bar, and a temperature of 240-360°C such as 300-360°C.
  • *MRE ZSM-48
  • MTT ZSM-23
  • TON ZSM-22
  • SAR silica- to-alumina ratio
  • the first reactor and second reactor set use a catalyst comprising a zeolite having a unidimensional (1-D) pore structure which is any of *MRE (ZSM-48), MTT (ZSM-23), TON (ZSM-22), or combinations thereof, as recited above.
  • the first and second reactor set use the same catalyst.
  • a reactor in the first reactor set and second reactor set operates at 1-25 bar, such as 1-15 bar, and at 260-360°C such as 300-360°C e.g. 320°C or 340°C.
  • the zeolite has a silica-to-alumina ratio (SAR) of up to 240.
  • SAR silica-to-alumina ratio
  • the zeolite has a SAR of up to 110, such as up to 100.
  • the zeolite has a SAR is higher than 10, for instance 15 or 20, or 30, 40, 50, 60, 70, 80, 90, 100.
  • the pressure is 2-25 bar, such as 2, 5, 10 or 12 or 17 or 20 or 22 bar. It has been found that while higher pressures (above 25 bar) increase the ratio of higher olefins to lower olefins i.e. higher selectivity to higher olefins, the higher pressures may also decrease the total yield of olefins (i.e. lower conversion of the oxygenate feed to olefins) and also increase the required temperature to achieve full conversion, which in turn creates the risk of less desired cracking reactions taking place.
  • the feedstock stream e.g. to the first reactor set is combined with a diluent, i.e. an inert diluent, such as nitrogen or carbon dioxide or a light paraffin such as methane, thereby reducing the exothermicity in the conversion to olefins, which is particularly preferred when the catalyst is arranged as a fixed bed.
  • a diluent i.e. an inert diluent, such as nitrogen or carbon dioxide or a light paraffin such as methane
  • the feedstock stream is methanol
  • it is diluted with e.g. nitrogen so that the methanol concentration in the feedstock is 2-20 vol.%, preferably 5-10 vol. %.
  • the invention provides therefore also a process whereby it is now possible to closely match the pressure of the MTO with the pressure of the subsequent Hydro/OLI, while still maintaining high conversion and an olefin stream (olefin product) which is ideal for subsequent oligomerization and/or Hydro/OLI.
  • the content of aromatics is about 2 wt% and 6 wt%, respectively.
  • the content of aromatics is about 1 wt% and 2 wt%, respectively.
  • the content of aromatics is about 1 wt% at both PMBOH.
  • the higher the PMBOH the higher the content of aromatics.
  • the higher independence of the aromatic content with respect to PM 6 OH at the lower MTO temperatures for instance at temperatures of 350°C or below, such as 340°C or 320°C or 300°C, enables also operation at the higher end of the pressures, e.g. 15, 20 or 25 bar. Not only are these pressures better matched to the downstream operations, e.g.
  • oligomerization or Hydro/OLI as mentioned above, but they are also closer to the pressures used in the upstream process, in particular methanol synthesis, which operates at high pressures, typically about 50-100 bar. Higher energy savings in terms of lower compression energy is thereby achieved, as so is a reduction in equipment size.
  • *MRE ZSM-48
  • MTT ZSM-23
  • TON ZSM-22
  • ZSM-48 when applied at said low temperatures, converts methanol to an olefin stream which is ideal for further oligomerization to jet fuel, particularly SAF in accordance with ASTM as defined above.
  • SAF jet fuel
  • Isoparaffins as well as the C3-C8 olefins, may also be oligomerized, so that in a way, instead of forming the unwanted ethylene and aromatics as byproducts, isoparaffins may be formed as a desired product.
  • the isoparaffins may optionally be separated for alkylation to increase octane number and then be incorporated into the gasoline pool, or simply be used as part of the olefin stream for downstream oligomerization.
  • the overall lifetime (number of cycles) of the catalyst is increased as an effect of the lower dealumination rate (affected by the combination of high temperature and water vapor produced during reaction). Further, the lifetime (during each cycle i.e.
  • cycle time of the catalyst is substantially increased, which without being bound by any theory, is probably an effect of the lower selectivity to aromatics due to less hydrogen transfer reactions.
  • the present invention will also enable a higher yield of desired products, e.g. C3-C8 olefins, since no or limited MeOH/DME cracking to methane occurs.
  • the features of the invention cooperate synergistically to bring about a superior process which is commercially applicable for conversion of the oxygenates to olefins and thereby for the subsequent downstream steps, e.g. oligomerization.
  • the weight hour space velocity (WHSV) is 0.5-12 h’ 1 , such as 1.5-10, or 4-10, for instance 6, 8, or 10 h’ 1 .
  • the weight hour space velocity (WHSV) in the first reactor set is higher than in the second reactor set. For instance, in the first reactor set where partial conversion of the oxygenate feedstock is intended, the WHSV is suitably 3 IT 1 or 6h' 1 while in the second reactor set where full conversion is intended the WHSV is suitably 2 h’ 1 .
  • first cycle in which precursor olefin compounds oligomerize
  • second cycle in which higher olefins cyclize and dehydrogenate to form aromatic compounds, which are maintained as active species at the intersection of pores in the zeolite. Due to the high WHSV, i.e. low residence times, the cycles are in a way interrupted already in the first cycle, thus significantly impeding even more the further formation of aromatic compounds. Accordingly, the present invention counterintuitively invites to not only increase the pressure and reduce the temperature, but also optionally to use a high space velocity, for instance in the first reactor set.
  • the catalyst is arranged as a fixed bed.
  • the feedstock comprises oxygenates derived from one or more oxygenates taken from the group consisting of triglycerides, fatty acids, resin acids, ketones, aldehydes or alcohols or ethers, where said oxygenates originate from one or more of a biological source, a gasification process, a pyrolysis process, Fischer-Tropsch synthesis, or methanol-based synthesis.
  • said one or more oxygenates are hydroprocessed oxygenates.
  • hydroprocessed oxygenates is meant oxygenates such as esters and fatty acids derived from hydroprocessing steps such as hydrotreating and hydrocracking.
  • the oxygenates are selected from methanol (MeOH), dimethyl ether (DME), or combinations thereof. These are particularly advantageous oxygenate feedstocks, as these are widely commercially available.
  • DME is more reactive than methanol and thus enables running the MTO step at lower temperatures, thereby increasing the selectivity for higher olefins.
  • conversion of DME releases only half the amount of water (steam) compared to methanol, thereby reducing the rate of (irreversible) deactivation due to steam-dealumination of the zeolite catalyst.
  • water is removed from the olefin stream produced in the MTO, since its presence may be undesirable when conducting the downstream oligomerization.
  • the methanol is made from synthesis gas prepared by using electricity from renewable sources such as wind or solar energy, e.g. eMethanolTM.
  • the synthesis gas is prepared by combining air separation, autothermal reforming or partial oxidation, and electrolysis of water, as disclosed in Applicant’s WO 2019/020513 A1 , or from a synthesis gas produced via electrically heated reforming as for instance disclosed in Applicant’s WO 2019/228797.
  • Applicant’s WO 2019/020513 A1 or from a synthesis gas produced via electrically heated reforming as for instance disclosed in Applicant’s WO 2019/228797.
  • the process of the invention further comprises, prior to passing the feedstock stream comprising oxygenates over a catalyst active in the conversion of oxygenates, in which the feedstock comprising oxygenates is a methanol stream i.e. methanol feed stream: producing said methanol feed stream by methanol synthesis of a methanol synthesis gas, wherein the methanol synthesis gas is generated by: steam reforming of a hydrocarbon feed such as natural gas, and/or at least partly by electrolysis of water and/or steam.
  • the methanol feed stream is produced from methanol synthesis gas which is generated by combining the use of water electrolysis in an alkaline or PEM electrolysis unit, or steam in a solid oxide electrolysis cell (SOEC) unit, thereby generating a hydrogen stream, together with the use of a CO2- rich stream in a SOEC unit for generating a stream comprising carbon monoxide and carbon dioxide, then combining the hydrogen stream and the stream comprising carbon monoxide and carbon dioxide for generating said methanol synthesis gas, as e.g. disclosed in Applicant’s co-pending European patent application No. 20216617.9.
  • the methanol synthesis gas is then converted into the methanol feed stream via a methanol synthesis reactor, as is well-known in the art.
  • process may also encompass the prior (front-end) production of the methanol feed stream, as recited above.
  • the process is conducted under the presence of hydrogen.
  • the hydrogen improves the methanol conversion by at least slightly decreasing the rate of deactivation of the catalyst, thereby also increasing catalyst lifetime.
  • there is no addition of hydrogen since this conveys a risk of hydrogenating some olefins and thereby decrease the olefin yield.
  • the process further comprises:
  • the process further comprises: passing at least a portion of the olefin stream e.g. after separating said isoparaffin stream, through an oligomerization step over an oligomerization catalyst, and optionally subsequently conducting a separation step, for thereby producing an oligomerized stream; and passing at least a portion of the oligomerized stream through a hydrogenation step over a hydrogenation catalyst, and optionally subsequently conducting a separation step, for thereby producing a hydrocarbon stream comprising hydrocarbons boiling in the jet fuel range.
  • the isoparaffins, as well as the C3-C8 olefins, may also be oligomerized.
  • the invention enables in a way, that instead of having unwanted aromatics as byproduct, isoparaffins are now provided as a desired product, which may optionally be separated for use as alkylation feed to increase octane number of gasoline optionally also produced in the process.
  • the provision of the isoparaffin stream separation step increases also flexibility in the selection of zeolites structures used in the oligomerization step.
  • the entire olefin stream passes through the oligomerization step.
  • the term “entire olefin stream” means at least 90 wt% of the stream.
  • the olefin stream e.g. the entire olefin stream after separating said isoparaffin stream
  • the oligomerization step i.e. the olefin stream is in direct fluid communication with the oligomerization step, or combined oligomerization and hydrogen step, as explained farther below.
  • the oligomerization step is preferably conducted by conventional methods including the use of an oligomerization catalyst such as solid phosphoric acid (“SPA”), ion-ex- change resins or a zeolite catalyst, for instance a conventional *MRE, BEA, FAU, MTT, TON, MFI and MTW catalyst, at a pressure of 30-100 bar, such as 50-100 bar, and a temperature of 100-350°C.
  • SPA solid phosphoric acid
  • BEA FAU
  • MTT ion-ex- change resins
  • a zeolite catalyst for instance a conventional *MRE, BEA, FAU, MTT, TON, MFI and MTW catalyst
  • the products from the oligomerization reaction may be subsequently separated in the separation step, such as distillation, thereby withdrawing a lighter hydrocarbon stream such as naphtha, which comprises C5-C7 hydrocarbons, and the oligomerized stream, which comprises C8+ hydrocarbons.
  • the hydrogenation step is preferably conducted by conventional methods including under the presence of hydrogen the use of a hydrotreating or hydrogenation catalyst, for instance a catalyst comprising one or more metals, e.g. Pd, Rh, Ru, Pt, Ir, Re, Co, Mo, Ni, W or combinations thereof, at a pressure of 60-70 bar and a temperature of 50- 350°C.
  • a hydrotreating or hydrogenation catalyst for instance a catalyst comprising one or more metals, e.g. Pd, Rh, Ru, Pt, Ir, Re, Co, Mo, Ni, W or combinations thereof, at a pressure of 60-70 bar and a temperature of 50- 350°C.
  • the C8+ hydrocarbons of the oligomerized stream are thereby saturated to form the corresponding paraffins.
  • These may be subsequently separated in a separation step, for instance a distillation step, whereby any hydrocarbons boiling in the diesel range are withdrawn and thereby separated from the hydrocarbons boiling in the jet fuel range i.e
  • the entire oligomerized stream passes through the hydrogenation step.
  • the term “entire oligomerized stream” means at least 90 wt% of the stream.
  • the hydrocarbon stream comprising hydrocarbons boiling in the jet fuel range is SAF, i.e. a sustainable aviation fuel in compliance with ASTM D7566 and ASTM D4054.
  • the oligomerization step and hydrogenation step are combined in a single hydro-oligomerization step (Hydro-OLI), e.g. by combining the steps in a single reactor.
  • Hydro-OLI hydro-oligomerization step
  • the oligomerization step and hydrogenation step are combined in a single hydro-oligomerization step, e.g. by combining the steps in a single reactor.
  • single hydro-oligomerization step or more generally “single step” or “single stage” means a section of the process in which no stream is withdrawn. Typically, a single stage does not include equipment such as compressors, by which the pressure is increased.
  • the oligomerization step is dimerization, optionally also trimerization, i.e. by conducting the oligomerization at conditions suitable for dimerization and/or trimerization.
  • the single reactor is preferably operated at a relatively low pressure, such as 15-60 bar, for instance 20-40 bar.
  • the oligomerization reaction is very exothermic per oligomerization step and much less heat is produced, - since there is only dimerization, optionally also trimerization - instead of higher oligomerization such as tetramerization or even pentamerization.
  • the lower heat produced favors approaching equilibrium, i.e. high conversion of olefins.
  • the oligomerization step converts the olefins to a mixture of mainly dimers, trimers and tetramers or even pentamers; for instance, a C6-olefin will result in a mixture comprising C12, C18, C24 products and probably also higher hydrocarbons.
  • a more selective and direct conversion of the higher olefins (C3-8 olefins incl. C4-C8 olefins) to the jet fuel relevant hydrocarbons, namely C8-C16, is obtained.
  • the dimerization and optional trimerization step comprises the use of lower pressures than in conventional oligomerization processes, thereby also reducing compression requirements which translates into higher energy efficiency - due to lower compression energy- as well as reduced costs, e.g. reduced costs of the oligomerization reactor and attendant equipment, as well as reduced operating costs due to less need of separating C16+ olefins otherwise formed in conventional OLI reactors. Accordingly, the pressure of the Hydro/OLI can be adapted to better match the pressure of the previous oxygenate conversion step.
  • the single hydro-oligomerization step is conducted in a single reactor having a stacked reactor bed where a first bed comprises an oligomerization catalyst, e.g. zeolite catalyst, and a subsequent bed comprises a hydrogenation catalyst.
  • the hydro-oligomerization step is conducted by reacting, under the presence of hydrogen, the olefin stream over a catalyst comprising a hydrogenation metal, such as a hydrogenation metal selected from Pd, Rh, Ru, Pt, Ir, Re, Co, Cu, Mo, Ni, W and combinations thereof, and preferably at a pressure of 15-60 bar such as 20-40 bar, and a temperature of 50-350°C, such as 100-250°C.
  • a hydrogenation metal such as a hydrogenation metal selected from Pd, Rh, Ru, Pt, Ir, Re, Co, Cu, Mo, Ni, W and combinations thereof, and preferably at a pressure of 15-60 bar such as 20-40 bar, and a temperature of 50-350°C, such as 100-250°C.
  • the catalyst comprises a zeolite having a structure selected from MFI, MEL, SZR, SVR, ITH, IMF, TUN, FER, EUO, MSE, *MRE, MWW, TON, MTT, FAU, AFO, AEL, and combinations thereof, preferably a zeolite with a framework having a 10-ring pore structure i.e. pore circumference defined by 10 oxygens, such as zeolites having a structure selected from TON, MTT, MFI, *MRE, MEL, AFO, AEL, EUO, FER, and combinations thereof.
  • the weight hour space velocity (WHSV) is 0.5-6 h’ 1 , such as 0.5-4 h’ 1 .
  • Lower pressures corresponding to the operating at conditions for dimerization, optionally also trimerization, are in particular 15-30 bar, such as 20-40 bar. This, again, is significantly lower than the pressures normally used in oligomerization, which typically are in the range 50-100 bar.
  • catalysts comprising NiW, for instance sulfide NiW (NiWS), or Ni such as Ni supported on a zeolite having a FAU or MTT structure, for instance a Y-zeolite, or ZSM-23.
  • NiW sulfide NiW
  • Ni such as Ni supported on a zeolite having a FAU or MTT structure, for instance a Y-zeolite, or ZSM-23.
  • the catalyst which is active for oligomerization and hydrogenation may for instance contain up to 50-80 wt% zeolite in a matrix/binder comprising an alumina component.
  • the hydrogenation metal may then be incorporated by impregnation on the catalyst.
  • the hydrogenation metals are selected so as to provide a moderate activity and thereby better control of the exothermicity of the oligomerization step by mainly hydrogenating the dimers being formed as the oligomerization takes place, thereby interrupting the formation of higher oligomers.
  • the present invention enables in a single hydro-oligomerization step the use of less equipment e.g. one single reactor, one type of catalyst, optionally a single separation stage downstream for obtaining the jet fuel.
  • a stream comprising C8-hydrocarbons resulting from cracked C9-C16 hydrocarbons is withdrawn from said hydrocarbon stream comprising hydrocarbons boiling in the jet fuel range and added to the other processes.
  • the process according to the first aspect of the invention cooperates with a refinery plant (or process), in particular a bio-refinery, and the stream comprising C8-hydrocarbons is added to the gasoline pool in a separate process for producing gasoline of said refinery.
  • a stream comprising C8- hydrocarbons resulting from cracked C9-C16 hydrocarbons is withdrawn from said hydrocarbon stream comprising hydrocarbons boiling in the jet fuel range and used (recycled) as additional feed stream to the oligomerization step or the single hydro-oligomerization step.
  • the invention in a second aspect, relates to a plant for producing an olefin stream from a feedstock comprising oxygenates, said plant being an oxygenate conversion section, such as MTO section, comprising: a first reactor set including a single reactor or several reactors, preferably mutually arranged in parallel, for the partial or full conversion of the oxygenates; and in series arrangement with the first reactor set, a second reactor set including a single reactor or several reactors, preferably mutually arranged in parallel, for the further conversion of the oxygenates, and a phase separation section arranged in between the first reactor set and the second reactor set, for thereby forming the olefin stream; wherein the first reactor set includes a single reactor or several reactors, preferably mutually arranged in parallel, adapted for receiving said feedstock comprising oxygenates and for the partial or full conversion of the oxygenates, thereby forming a raw olefin stream comprising unconverted oxygenates and C2-C8 olefins;
  • the phase separation section comprises in particular a three-phase separator, arranged downstream the first reactor set, said phase separation section being adapted for receiving said raw olefin stream and forming: a first olefin stream, which is rich in lower olefins, particularly C2-C3 olefins; a separated oxygenate stream comprising the unconverted oxygenates, e.g. the separated oxygenate stream may comprise water and methanol; a second olefin stream, which is rich in higher olefins, particularly C3-C8 olefins incl. C4-C8 olefins;
  • a mixing device e.g. a mixing unit, for combining the first olefin stream with the separated oxygenate stream comprising the unconverted oxygenates, thereby forming a combined stream comprising lower olefins, particularly C2-C3 olefins, and the unconverted oxygenates;
  • the second reactor set includes a single reactor or several reactors, preferably mutually arranged in parallel, and arranged downstream said phase separation section, adapted for receiving said combined stream, thereby forming a third olefin stream which is rich in higher olefins, particularly C3-C8 olefins incl. C4-C8 olefins;
  • a mixing device e.g. a mixing unit, for combining the second olefin stream (which may be regarded as a by-pass stream of the second reactor set) with the third olefin stream, thereby forming said olefin stream.
  • a compressor is preferably arranged therein, e.g. downstream the mixing device, for boosting the pressure of the combined stream to the pressure of a downstream unit, such as the pressure of the second reactor set, or the pressure required in an optional downstream oligomerization and hydrogenation of the olefin stream.
  • an oxygenate conversion section 200 such as MTO section
  • an oligomerization and hydrogenation section 300 for further conversion into jet fuel.
  • a feedstock stream 100 comprising oxygenates such as methanol and/or DME passes through a first reactor set 200’, for instance 3 reactors arranged in parallel, for thereby achieving 50-70% conversion of the methanol and producing a raw olefin stream 105 comprising water, methanol and olefins e.g. C2-C8 olefins.
  • the raw olefin stream 105 is subjected to separation in a 3-phase separator 200” thereby producing a first olefin stream 105a, which is rich in lower olefins, particularly C2-C3 olefins or mainly C2-olefins (ethylene), a separated oxygenate stream 105b comprising the unconverted oxygenates (unconverted methanol), and a second olefin stream 105c which is rich in higher olefins, particularly C3-C8 olefins incl. C4-C8 olefins.
  • the first olefin stream 105a is combined with the separated oxygenate stream 105b comprising the unconverted oxygenates, thereby forming a combined stream 105d comprising lower olefins, particularly C2-C3 olefins or mainly ethylene, and the unconverted oxygenates.
  • This combined stream is pressurized and fed to a second reactor set 200”’ arranged downstream, and which may for instance include two reactors arranged in parallel, for thereby achieving full conversion e.g. 85% or 90% or higher.
  • the first reactor set 200’ and second reactor set 200’” are thereby arranged in series.
  • a third olefin stream 105e is produced which is rich in higher olefins, particularly C3-C8 olefins incl. C4-C8 olefins.
  • the second olefin stream 105c (bypass stream) is combined with the third olefin stream 105e, thereby forming said olefin stream 106 which may have been pressurized.
  • the resulting olefin stream 106 is optionally further converted (as shown by the stippled lines) in a downstream oligomerization and hydrogenation section 300, which is combined as a single hydro-oligomerization step, for instance in a single reactor, thereby producing a hydrocarbon stream 112 comprising hydrocarbons boiling in the jet fuel range (C8-C16), particularly SAF.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé et une installation de production d'un flux d'oléfines, comprenant le passage d'un flux de charge d'alimentation comportant des composés oxygénés sur un catalyseur, pour former un flux d'oléfines ; l'utilisation d'un premier ensemble de réacteurs comportant un seul réacteur ou plusieurs réacteurs pour la conversion partielle ou complète des composés oxygénés ; et dans une disposition en séries avec le premier ensemble de réacteurs, l'utilisation d'un second ensemble de réacteurs comportant un seul réacteur ou plusieurs réacteurs, pour la conversion supplémentaire des composés oxygénés, et une étage de séparation de phase entre le premier ensemble de réacteurs et le second ensemble de réacteurs, pour ainsi former le flux d'oléfines.
PCT/EP2021/076372 2020-09-25 2021-09-24 Procédé de conversion alternatif du méthanol en oléfines (mto) WO2022063993A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP21782977.9A EP4217446A1 (fr) 2020-09-25 2021-09-24 Procédé de conversion alternatif du méthanol en oléfines (mto)
US18/245,828 US20240026236A1 (en) 2020-09-25 2021-09-24 Alternative methanol to olefin (MTO) process
CN202180064887.9A CN116194557A (zh) 2020-09-25 2021-09-24 可替代的甲醇制烯烃(mto)工艺

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DKPA202001109 2020-09-25
DKPA202001109 2020-09-25

Publications (1)

Publication Number Publication Date
WO2022063993A1 true WO2022063993A1 (fr) 2022-03-31

Family

ID=80846269

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2021/076372 WO2022063993A1 (fr) 2020-09-25 2021-09-24 Procédé de conversion alternatif du méthanol en oléfines (mto)

Country Status (4)

Country Link
US (1) US20240026236A1 (fr)
EP (1) EP4217446A1 (fr)
CN (1) CN116194557A (fr)
WO (1) WO2022063993A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023196327A1 (fr) * 2022-04-06 2023-10-12 ExxonMobil Technology and Engineering Company Procédés de conversion d'oléfines c2+ en oléfines à nombre de carbones plus élevé, utiles pour la production de compositions de kérosène isoparaffinique
US12012562B2 (en) 2022-04-06 2024-06-18 ExxonMobil Technology and Engineering Company Methods for converting C2+ olefins to higher carbon number olefins useful in producing isoparaffinic distillate compositions

Citations (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4021502A (en) 1975-02-24 1977-05-03 Mobil Oil Corporation Converting low molecular weight olefins over zeolites
US4211640A (en) 1979-05-24 1980-07-08 Mobil Oil Corporation Process for the treatment of olefinic gasoline
US4227992A (en) 1979-05-24 1980-10-14 Mobil Oil Corporation Process for separating ethylene from light olefin mixtures while producing both gasoline and fuel oil
US4433185A (en) 1983-04-04 1984-02-21 Mobil Oil Corporation Two stage system for catalytic conversion of olefins with distillate and gasoline modes
US4456779A (en) 1983-04-26 1984-06-26 Mobil Oil Corporation Catalytic conversion of olefins to higher hydrocarbons
US4476338A (en) 1983-06-02 1984-10-09 Mobil Oil Corporation Olefins from methanol and/or dimethyl ether
US4523046A (en) * 1982-02-25 1985-06-11 Mobil Oil Corporation Method for gasoline yield enhancement in the fixed bed methanol-to-gasoline process
US4613719A (en) 1985-10-17 1986-09-23 Phillips Petroleum Company Oligomerization of olefins
US4740645A (en) * 1984-09-14 1988-04-26 Mobil Oil Corporation Multistage conversion of lower olefins with interreactor quenching
US4898717A (en) * 1984-01-04 1990-02-06 Mobil Oil Corp. Multistage process for converting oxygenates to distillate hydrocarbons with interstage ethene recovery
US5177179A (en) 1991-04-04 1993-01-05 E. I. Du Pont De Nemours And Company Perfluoroalkylated diaminomesitylene and polyimides therefrom
US5177279A (en) 1990-10-23 1993-01-05 Mobil Oil Corporation Integrated process for converting methanol to gasoline and distillates
US7482300B2 (en) 2005-12-13 2009-01-27 Exxonmobil Research And Engineering Company High activity ZSM-48 and methods for dewaxing
US8524970B2 (en) 2007-05-11 2013-09-03 Lurgi Gmbh Process and plant for producing synthetic fuels
WO2014008337A1 (fr) * 2012-07-03 2014-01-09 David Bradin Procédé de fabrication de compositions de carburéacteur renouvelable
CN104059682A (zh) * 2014-06-24 2014-09-24 东南大学 生物质选择性热解-梯级转化制备航空燃油的装置和方法
US20170121237A1 (en) 2015-10-28 2017-05-04 Exxonmobil Research And Engineering Company Methods and apparatus for converting oxygenate-containing feedstocks to gasoline and distillates
WO2018071905A1 (fr) 2016-10-14 2018-04-19 Gevo, Inc. Conversion de mélanges d'oléfines en c2-c8 en carburéacteur et/ou en carburant diesel avec un rendement élevé à partir d'alcools d'origine biologique
US9957449B2 (en) 2015-04-24 2018-05-01 Uop Llc Process for the production of jet-range hydrocarbons by oligomerization of renewable olefins having 3 to 8 carbons
WO2019020513A1 (fr) 2017-07-25 2019-01-31 Haldor Topsøe A/S Méthode de préparation d'un gaz de synthèse
US20190176136A1 (en) 2016-09-30 2019-06-13 Haldor Topsøe A/S Catalyst comprising small 10-ring zeolite crystallites and a method for producing hydrocarbons by reaction of oxygenates over said catalyst
WO2019158687A1 (fr) * 2018-02-16 2019-08-22 Chemieanlagenbau Chemnitz Gmbh Procédé et installation de production d'une essence synthétique
WO2019228797A1 (fr) 2018-05-31 2019-12-05 Haldor Topsøe A/S Reformage à la vapeur chauffé par chauffage par résistance

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4684757A (en) * 1986-07-18 1987-08-04 Mobil Oil Corporation Process for converting methanol to alkyl ethers, gasoline, distillate and alkylate liquid hydrocarbons
WO2018106397A1 (fr) * 2016-12-07 2018-06-14 Exxonmobil Research And Engineering Company Conversion combinée d'oléfines et de composés oxygénés pour la production d'aromatiques

Patent Citations (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4021502A (en) 1975-02-24 1977-05-03 Mobil Oil Corporation Converting low molecular weight olefins over zeolites
US4211640A (en) 1979-05-24 1980-07-08 Mobil Oil Corporation Process for the treatment of olefinic gasoline
US4227992A (en) 1979-05-24 1980-10-14 Mobil Oil Corporation Process for separating ethylene from light olefin mixtures while producing both gasoline and fuel oil
US4523046A (en) * 1982-02-25 1985-06-11 Mobil Oil Corporation Method for gasoline yield enhancement in the fixed bed methanol-to-gasoline process
US4433185A (en) 1983-04-04 1984-02-21 Mobil Oil Corporation Two stage system for catalytic conversion of olefins with distillate and gasoline modes
US4456779A (en) 1983-04-26 1984-06-26 Mobil Oil Corporation Catalytic conversion of olefins to higher hydrocarbons
US4476338A (en) 1983-06-02 1984-10-09 Mobil Oil Corporation Olefins from methanol and/or dimethyl ether
US4898717A (en) * 1984-01-04 1990-02-06 Mobil Oil Corp. Multistage process for converting oxygenates to distillate hydrocarbons with interstage ethene recovery
US4740645A (en) * 1984-09-14 1988-04-26 Mobil Oil Corporation Multistage conversion of lower olefins with interreactor quenching
US4613719A (en) 1985-10-17 1986-09-23 Phillips Petroleum Company Oligomerization of olefins
US5177279A (en) 1990-10-23 1993-01-05 Mobil Oil Corporation Integrated process for converting methanol to gasoline and distillates
US5177179A (en) 1991-04-04 1993-01-05 E. I. Du Pont De Nemours And Company Perfluoroalkylated diaminomesitylene and polyimides therefrom
US7482300B2 (en) 2005-12-13 2009-01-27 Exxonmobil Research And Engineering Company High activity ZSM-48 and methods for dewaxing
US8524970B2 (en) 2007-05-11 2013-09-03 Lurgi Gmbh Process and plant for producing synthetic fuels
WO2014008337A1 (fr) * 2012-07-03 2014-01-09 David Bradin Procédé de fabrication de compositions de carburéacteur renouvelable
CN104059682A (zh) * 2014-06-24 2014-09-24 东南大学 生物质选择性热解-梯级转化制备航空燃油的装置和方法
US9957449B2 (en) 2015-04-24 2018-05-01 Uop Llc Process for the production of jet-range hydrocarbons by oligomerization of renewable olefins having 3 to 8 carbons
US20170121237A1 (en) 2015-10-28 2017-05-04 Exxonmobil Research And Engineering Company Methods and apparatus for converting oxygenate-containing feedstocks to gasoline and distillates
US20190176136A1 (en) 2016-09-30 2019-06-13 Haldor Topsøe A/S Catalyst comprising small 10-ring zeolite crystallites and a method for producing hydrocarbons by reaction of oxygenates over said catalyst
WO2018071905A1 (fr) 2016-10-14 2018-04-19 Gevo, Inc. Conversion de mélanges d'oléfines en c2-c8 en carburéacteur et/ou en carburant diesel avec un rendement élevé à partir d'alcools d'origine biologique
WO2019020513A1 (fr) 2017-07-25 2019-01-31 Haldor Topsøe A/S Méthode de préparation d'un gaz de synthèse
WO2019158687A1 (fr) * 2018-02-16 2019-08-22 Chemieanlagenbau Chemnitz Gmbh Procédé et installation de production d'une essence synthétique
WO2019228797A1 (fr) 2018-05-31 2019-12-05 Haldor Topsøe A/S Reformage à la vapeur chauffé par chauffage par résistance

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CH. BAERLOCHERL.B. MCCUSKERD.H. OLSON, ATLAS OF ZEOLITE FRAMEWORK TYPES, 2007
TEKETEL SHEWANGIZAW ET AL: "Co-conversion of methanol and light alkenes over acidic zeolite catalyst H-ZSM-22: Simulated recycle of non-gasoline range products", APPLIED CATALYSIS A: GENERAL, ELSEVIER, AMSTERDAM, NL, vol. 494, 31 January 2015 (2015-01-31), pages 68 - 76, XP029142249, ISSN: 0926-860X, DOI: 10.1016/J.APCATA.2015.01.035 *
YARULINA ET AL., CHEMCATCHEM, vol. 8, 2016, pages 3057 - 3063
YARULINA IRINA ET AL: "Cover Picture: Suppression of the Aromatic Cycle in Methanol-to-Olefins Reaction over ZSM-5 by Post-Synthetic Modification Using Calcium (ChemCatChem 19/2016)", vol. 8, no. 19, 6 October 2016 (2016-10-06), DE, pages 3003 - 3003, XP055775530, ISSN: 1867-3880, Retrieved from the Internet <URL:https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fcctc.201601185> DOI: 10.1002/cctc.201601185 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023196327A1 (fr) * 2022-04-06 2023-10-12 ExxonMobil Technology and Engineering Company Procédés de conversion d'oléfines c2+ en oléfines à nombre de carbones plus élevé, utiles pour la production de compositions de kérosène isoparaffinique
US12012562B2 (en) 2022-04-06 2024-06-18 ExxonMobil Technology and Engineering Company Methods for converting C2+ olefins to higher carbon number olefins useful in producing isoparaffinic distillate compositions
US12012561B2 (en) 2022-04-06 2024-06-18 ExxonMobil Technology and Engineering Company Methods for converting C2+ olefins to higher carbon number olefins
US12084622B2 (en) 2022-04-06 2024-09-10 ExxonMobil Technology and Engineering Company Methods for converting C2+ olefins to higher number olefins useful in producing isoparaffinic kerosene compositions

Also Published As

Publication number Publication date
EP4217446A1 (fr) 2023-08-02
US20240026236A1 (en) 2024-01-25
CN116194557A (zh) 2023-05-30

Similar Documents

Publication Publication Date Title
US20230340335A1 (en) Methanol to jet fuel (MTJ) process
CN112912471B (zh) 联合生产航空燃料和柴油的方法
US20230365871A1 (en) Methanol to olefin (MTO) process
EP1228166B1 (fr) Procede en une etape, permettant de transformer des composes oxygenes en essence et en distillat, en presence de zeolite cyclique a dix elements unidimensionnel
CN102725379B (zh) 将甲醇转化为轻质烯烃、汽油和馏分油的方法和系统
US10190059B2 (en) Process for the hydrotreatment of renewable materials, with an optimized gas recycle
CN107148461A (zh) 将乙烯原料转化为烃燃料的系统和方法
US8513476B2 (en) Process for producing light olefins from a feed containing triglycerides
US20240026236A1 (en) Alternative methanol to olefin (MTO) process
CN107075385A (zh) 将乙烯原料转化为烃燃料的系统和方法
CN102665903A (zh) 由杂原子有机化合物生产c10+烃的方法
US20110098494A1 (en) Method of hydrotreating feeds from renewable sources with indirect heating using a catalyst based on nickel and molybdenum having a particular atomic ratio
CA3184973A1 (fr) Procede et installation de production d&#39;essence a partir d&#39;une charge renouvelable
CA3236227A1 (fr) Procede et installation pour ameliorer la conversion de composes oxygenes en essence
US20240124783A1 (en) Process and plant for converting oxygenates to gasoline with improved gasoline yield and octane number as well as reduced durene levels
WO2022063995A1 (fr) Procédé de conversion méthanol en oléfine (mto)
WO2023138876A1 (fr) Procédé et installation de conversion de composés oxygénés
WO2023186736A1 (fr) Procédé et installation de production d&#39;hydrocarbures à partir d&#39;un gaz comprenant du co2
US20240182794A1 (en) Process and plant for improving gasoline yield and octane number
KR20240090397A (ko) 수송 연료의 생산 방법
KR20240130078A (ko) 함산소 공급원료를 탄화수소 분획 및 다른 적용들로 업그레이드하는 공정
WO2024200429A1 (fr) Procédé et installation destinés à la conversion de composés oxygénés en hydrocarbures en c5+ bouillant dans la plage d&#39;ébullition de carburéacteur

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21782977

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 18245828

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2021782977

Country of ref document: EP

Effective date: 20230425